Catalytic and stoichiometric oxidation of N,N-dimethylanilines mediated by nonheme oxoiron(IV) complex with tetrapyridyl ligand

Lakk-Bogáth, Dóra; Kripli, Balázs; Meena, Bashdar I.; Speier, Gábor; Kaizer, József

doi:10.1016/j.poly.2019.05.025

Cited by 8 publications

(14 citation statements)

References 39 publications

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“…Additionally, H-atom abstraction from 4-Me-DMA proceeded at a similar rate with a second-order rate constant k 2 = 0.008 M −1 s −1 at 278 K is noticeably faster than with [Fe IV (N4Py*)(O)] 2+ ‡/4Me-DMA system (9.8 ± 0.4) × 10 −2 M −1 s −1 at 298 K) reported recently (Table S9 †). 15 The relative reactivity of 6 toward the electrophilic and nucleophilic model compounds shows the order BA > 4Me-DMA > PAA > 2,6-DTBP (Fig. 5).…”

Section: Communication Dalton Transactionsmentioning

confidence: 97%

A nonheme peroxo-diiron(iii) complex exhibiting both nucleophilic and electrophilic oxidation of organic substrates

et al. 2021

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Section: Communication Dalton Transactionsmentioning

confidence: 97%

A nonheme peroxo-diiron(iii) complex exhibiting both nucleophilic and electrophilic oxidation of organic substrates

et al. 2021

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“…N -dealkylation reactions represent an important type of biochemical reaction . Besides their occurrence in DNA repair, , the N -dealkylation of tertiary amines, and in particular N -demethylation, is one of the main reactions in the metabolism of xenobiotics. , …”

Section: Introductionmentioning

confidence: 99%

“…This metabolic process removes chemicals that contain tertiary amines and are foreign to the body through an oxidative pathway. N -dealkylation is commonly catalyzed by monooxygenases such as cytochrome P450 , and typically proceeds through intermediacy of iron-oxo species. , …”

Section: Introductionmentioning

confidence: 99%

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Mild and Functional Group-Tolerant Aerobic N-Dealkylation of Tertiary Amines Promoted by Photoredox Catalysis

Yılmaz

Emmert

2023

J. Org. Chem.

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This article describes the development of a mild method for the N-dealkylation of tertiary amines via photoredox catalysis and its application in late-stage functionalization. Using the developed method, more than 30 diverse aliphatic, aniline-type, and complex substrates are shown to undergo N-dealkylation, providing a method with broader functional group tolerance compared to methods found in the literature. The scope also includes tertiary and secondary amine molecules with complex substructures and drug substrates. Interestingly, α-oxidation to imines was observed in several cyclic substructures instead of N-dealkylation, suggesting that imines are relevant reaction intermediates.

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“…Due to the increasing importance of catalase activity, we have focused on the development of such a non-heme iron-containing system that shows catalase-like activity in aqueous solution. To get more insight into the mechanism of H 2 O 2 dismutation the mononuclear complex [Fe II (N4Py*)(CH 3 CN)](CF 3 SO 3 ) 2 (1) (N4Py* = N , N -bis(2-pyridylmethyl)-1,2-di(2-pyridyl)ethylamine) was chosen as a catalyst, where the possible reactive intermediates high-valent Fe IV =O (2) and Fe III -OOH (3) are known and spectroscopically well characterized (Scheme 1) [43,44,45,46].…”

Section: Introductionmentioning

confidence: 99%

Stability and Catalase-Like Activity of a Mononuclear Non-Heme Oxoiron(IV) Complex in Aqueous Solution

et al. 2019

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Heme-type catalase is a class of oxidoreductase enzymes responsible for the biological defense against oxidative damage of cellular components caused by hydrogen peroxide, where metal-oxo species are proposed as reactive intermediates. To get more insight into the mechanism of this curious reaction a non-heme structural and functional model was carried out by the use of a mononuclear complex [FeII(N4Py*)(CH3CN)](CF3SO3)2 (N4Py* = N,N-bis(2-pyridylmethyl)- 1,2-di(2-pyridyl)ethylamine) as a catalyst, where the possible reactive intermediates, high-valent FeIV=O and FeIII–OOH are known and spectroscopically well characterized. The kinetics of the dismutation of H2O2 into O2 and H2O was investigated in buffered water, where the reactivity of the catalyst was markedly influenced by the pH, and it revealed Michaelis–Menten behavior with KM = 1.39 M, kcat = 33 s−1 and k2(kcat/KM) = 23.9 M−1s−1 at pH 9.5. A mononuclear [(N4Py)FeIV=O]2+ as a possible intermediate was also prepared, and the pH dependence of its stability and reactivity in aqueous solution against H2O2 was also investigated. Based on detailed kinetic, and mechanistic studies (pH dependence, solvent isotope effect (SIE) of 6.2 and the saturation kinetics for the initial rates versus the H2O2 concentration with KM = 18 mM) lead to the conclusion that the rate-determining step in these reactions above involves hydrogen-atom transfer between the iron-bound substrate and the Fe(IV)-oxo species.

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Catalytic and stoichiometric oxidation of N,N-dimethylanilines mediated by nonheme oxoiron(IV) complex with tetrapyridyl ligand

Cited by 8 publications

References 39 publications

A nonheme peroxo-diiron(iii) complex exhibiting both nucleophilic and electrophilic oxidation of organic substrates

A nonheme peroxo-diiron(iii) complex exhibiting both nucleophilic and electrophilic oxidation of organic substrates

Mild and Functional Group-Tolerant Aerobic N-Dealkylation of Tertiary Amines Promoted by Photoredox Catalysis

Stability and Catalase-Like Activity of a Mononuclear Non-Heme Oxoiron(IV) Complex in Aqueous Solution

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